CN104032095B - A kind of method of liquid steel dephosphorization agent and liquid steel dephosphorization - Google Patents
A kind of method of liquid steel dephosphorization agent and liquid steel dephosphorization Download PDFInfo
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Abstract
The invention discloses a kind of method of liquid steel dephosphorization agent and liquid steel dephosphorization.The method of described liquid steel dephosphorization is included in converter tapping process, molten state treated that dephosphorization molten steel contacts with liquid steel dephosphorization agent, and product of contact is transferred in LF stove carries out dephosphorization, skim after dephosphorization completes, wherein, described liquid steel dephosphorization agent contains lime and bauxitic clay; And with the gross weight of described liquid steel dephosphorization agent for benchmark, the content of described lime is 80-98 % by weight, the content of described bauxitic clay is 2-20 % by weight; And the Argon intensity in LF stove is at least 100Nm
3/ h ton molten steel.Adopt liquid steel dephosphorization agent provided by the invention to carry out dephosphorization under specific Argon intensity, significantly can reduce the phosphorus content in molten steel, the dephosphorization rate of molten steel is improved, has prospects for commercial application.
Description
Technical field
The present invention relates to a kind of liquid steel dephosphorization agent and use this liquid steel dephosphorization agent to carry out the method for liquid steel dephosphorization.
Background technology
In iron and steel the detrimental impurity such as phosphorous, sulphur be directly connected to the performance of iron and steel, wherein in steel, the existence of phosphorus can reduce the plasticity of steel.When phosphorus content height in steel, steel are easy to " cold short phenomenon " occurs, and in metallurgical production, reduce the phosphorus content in steel by dephosphorization, and the plasticity toughness of steel will be improved, and significantly can improve the mechanical property of steel.
Along with expanding economy, the requirement of modern society to ferrous materials performance improves day by day, this means the control of Impurities in steel more and more stricter.Making great efforts to remove the impurity in steel, the steel producing low impurity content and Clean Steel is iron and steel enterprise's vital task.And the particular requirement of Clean Steel will be reached, secondary refining must be adopted in Iron and Steel Production.
In convertor steelmaking process, due to the good dephosphorization thermodynamic condition that it possesses, therefore, during tapping, in molten steel, the content of phosphorus is lower, and dephosphorization rate can reach about 90%.But owing to being with the reason such as slag and molten steel alloying during converter tapping, thermodynamic condition changes, now easily there is rephosphorization phenomenon, phosphorus content in molten steel is caused to increase, and ultra-low phosphoretic steel in Clean Steel requires that the phosphorus content [P] in steel reaches the≤level of 0.005 % by weight, so, must pass through the steel that secondary refining dephosphorization just can be met requirement.Research about secondary refining dephosphorization is the technical guarantee of producing ultra-low phosphoretic steel, but is found by literature survey, and the domestic and international research carried out in secondary refining dephosphorization is little at present.
CN102618689A discloses a kind of method of high efficiency, low cost producing ultra-low phosphorous steel by converter water, and the method comprises the molten iron containing P≤0.11%, Si0.3-0.5%, Mn0.3-0.6%, temperature 1260-1350 DEG C is entered converter; Add slag charge, argon bottom-blowing, flow>=0.07Nm
3/ tmin, top blast oxygen, oxygen pressure≤0.8MPa, bath temperature≤1450 DEG C, in earlier stage duration of blast 7-10min, deslagging 1/3-1/2; Adopt high rifle bit manipulation mid-term, add slag charge, control molten steel [C] 0.30-0.60%, bath temperature 1520-1560 DEG C, again deslagging 40%-60%; Later stage adds lime 2-5kg/t steel, and refrigerant consumption is 2-5kg/t steel, adopts atm number argon bottom-blowing to stir, churning time>=1.5min, then adopts lowly to rob bit manipulation, as terminal C=0.025-0.08%, taps during bath temperature 1600-1630 DEG C; Produce the ultra-low phosphoretic steel water of phosphorus content≤50ppm.But when adopting the method for this patent application to carry out the production of molten steel, owing to being with the reason such as slag and molten steel alloying during converter tapping, thermodynamic condition changes, and there will be rephosphorization phenomenon, cause phosphorus content in molten steel to increase, therefore practical function is limited.
CN101319262A discloses a kind of method of manufacturing ultra-low phosphoretic steel with outside-stove refining dephosphorization of liquid steel, and the method comprises 1. converter tapping: tapping temperature is at 1550-1660 DEG C, and during tapping, phosphorus content is below 0.02 % by weight, adopts non-deoxidation, pushing off the slag process tapping; 2. first dephosphorization: flow in ladle with steel during converter tapping and add Dephosphorising flux, add-on is 5-20kg/t; Described dephosphorization solvent is prepared from by specified weight per-cent by following raw material: CaO20-80%, FeO10-15%, CaF
20-40%; 3. deep dephosphorization: the position regulating tremie pipe and downtake, makes it the heteropleural being in tremie pipe, ladle is transported to RH station, and vacuumizes, drops into composite sphere from RH high hopper, circulation 0.1-15min; 4. skim: vacuum breaker, to skim, then add ladle covering agent; 5. heated and stirred: carry out heated and stirred at refining furnace, molten steel heating and temperature control is at 1580-1620 DEG C; 6. deoxidation, alloying refining treatment: 7. continuous casting: continuous casting adopts whole process protection cast.When adopting the method for this patent application to carry out the production of molten steel, due to after adding Dephosphorising flux, directly add RH station and process, inevitable like this reaction between carbon and oxygen deoxidation will occur, therefore rephosphorization can occur under reducing atmosphere, practical effect is very limited.
CN101104876A discloses a kind of method of producing ultra-low phosphoretic steel by molten steel dephosphorising outside furnace, the method is carried out according to following steps: be 1. less than 0.013% tapping with weight percent end phosphorus content during converter tapping, flows in ladle add Dephosphorising flux when tapping with steel; Described dephosphorization solvent is overbasic dephosphorization solvent, by weight percentage consist of lime 60-75%, fluorite 10-25% and ferric oxide 0-20%; 2. slag-stopping tapping is adopted during tapping, non-deoxidation tapping; 3., after having tapped, the dephosphorized slag in ladle is removed; 4. carry out again after skimming heating, deoxidation alloying, the refining treatment such as desulfurization; 5. then continuous casting is carried out.This patent application utilizes dephosphorization in tapping process, do not increase the dephosphorization treatment time, easy to use, dephosphorization efficiency is high, the treatment time is short, dephosphorization effect is stable, the dephosphorization requirement of different ultra-low phosphorus molten steel can be met, but the method only adds Dephosphorising flux at tapping process, stir without any rear operation Argon and just skim, actual dephosphorization effect is limited.
Summary of the invention
The object of the invention is in order to overcome adopt existing method to carry out dephosphorization to molten steel time dephosphorization rate lower defect, and a kind of new liquid steel dephosphorization agent is provided and adopts this liquid steel dephosphorization agent under specific Argon intensity, carry out the method for liquid steel dephosphorization.
Particularly, the invention provides a kind of liquid steel dephosphorization agent, wherein, described liquid steel dephosphorization agent contains lime and bauxitic clay, and with the gross weight of described liquid steel dephosphorization agent for benchmark, the content of described lime is 80-98 % by weight, the content of described bauxitic clay is 2-20 % by weight.
In addition, present invention also offers a kind of method of liquid steel dephosphorization, the method is included in converter tapping process, molten state treated that dephosphorization molten steel contacts with liquid steel dephosphorization agent, and product of contact is transferred in LF stove carries out dephosphorization, skim after dephosphorization completes, wherein, described liquid steel dephosphorization agent is above-mentioned liquid steel dephosphorization agent, and in dephosphorizing process, the Argon intensity in LF stove is at least 100Nm
3/ h ton molten steel.
The present inventor is surprised to find that under study for action, in converter tapping process, that the liquid steel dephosphorization agent of the lime of content certain content and bauxitic clay is added to molten state treats in dephosphorization molten steel, and ensure that the molten steel after adding liquid steel dephosphorization agent carries out large stir process with specific Argon intensity in LF stove, significantly can reduce the phosphorus content in molten steel, the dephosphorization rate of molten steel is improved.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
Liquid steel dephosphorization agent provided by the invention contains lime and bauxitic clay, and with the gross weight of described liquid steel dephosphorization agent for benchmark, the content of described lime is 80-98 % by weight, and the content of described bauxitic clay is 2-20 % by weight; Preferably, with the gross weight of described liquid steel dephosphorization agent for benchmark, the content of described lime is 90-95 % by weight, the content of described bauxitic clay is 5-10 % by weight, is controlled to make these two kinds of materials play better collaborative dephosphorizing in above-mentioned preferred scope by the content of described lime and bauxitic clay.
The inorganic materials of described lime to be a kind of with calcium oxide be main component.In liquid steel dephosphorization process, described lime mainly plays the effect regulating molten steel alkalescence.Although existing all lime all to can be used in the present invention and can play dephosphorizing with described bauxitic clay coordinated, but in order to obtain higher dephosphorization rate, preferably, with the gross weight of described lime for benchmark, containing the CaO of at least 95 % by weight in described lime, all the other are CaCO
3.
According to liquid steel dephosphorization agent provided by the invention, described lime uses with the form of solid particulate usually.The grain graininess of the present invention to described lime is not particularly limited, preferably, the grain graininess of described lime is less than 30mm, and the grain graininess of at least 80 % by weight is 5-20mm in described lime, the grain graininess of described lime is controlled can ensure that it has good melting properties in above-mentioned preferred scope, thus improve dephosphorization rate further.
In the present invention, described grain graininess refers on particle between any two differences maximum linear distance.Such as, when described particle is spherical, described grain graininess refers to its diameter.
Described vanadium alum clay is also known as alumina or bauxite, and its main component is Al
2o
3.Although existing various bauxitic clay all can be used in the present invention, if Al in described bauxitic clay
2o
3content lower, be then unfavorable for the raising of dephosphorization rate, and usually containing a certain amount of impurity in described bauxitic clay, therefore, consider from the raising of liquid steel dephosphorization rate and the ready availability angle of bauxitic clay raw material, preferably, with the gross weight of described bauxitic clay for benchmark, Al in described bauxitic clay
2o
3content be 80-85 % by weight, all the other are SiO
2.
The method of liquid steel dephosphorization provided by the invention is included in converter tapping process, molten state treated that dephosphorization molten steel contacts with liquid steel dephosphorization agent, and product of contact is transferred in LF stove carries out dephosphorization, dephosphorization is skimmed after completing, wherein, described liquid steel dephosphorization agent is above-mentioned liquid steel dephosphorization agent, and the Argon intensity in LF stove is at least 100Nm
3/ h ton molten steel.
Term " Argon intensity " used in this specification sheets refers to that its unit is Nm in the Argon amount of blowing molten steel per ton in the unit time
3/ h ton molten steel.
As well known to those skilled in the art, in smelting molten steel process, first molten steel is bessemerized, and then molten steel converter tapping is moved in LF stove carry out refining.Described molten state treated that the mode that dephosphorization molten steel contacts with liquid steel dephosphorization agent can be selected for the routine of this area, usually can in converter tapping process, treat that dephosphorization steel flow adds liquid steel dephosphorization agent with molten state, both flow in LF stove together and carry out Argon dephosphorization afterwards.
The method of liquid steel dephosphorization provided by the invention is applicable to the dephosphorizing process of current described molten steel, is particularly suitable for carrying out dephosphorization to ultra-low phosphoretic steel water, that is, treat described in that the phosphorus content of dephosphorization molten steel is preferably 0.01-0.03 % by weight.
According to the method for liquid steel dephosphorization provided by the invention, in order to ensure that the oxidisability of molten steel is to be down to lower level by phosphorus content wherein, preferably, treat the oxygen activity >=500ppm of dephosphorization molten steel to be more preferably 800-1000ppm described in.Term " oxygen activity " refers to the weight concentration of the oxygen molecule be dissolved in molten steel, and unit is ppm.In the present invention, describedly treat that the oxygen activity of dephosphorization molten steel according to well known to a person skilled in the art that various method measures, such as, can measure according to oxygen sensor with solid electrolyte technology, concrete test process is known to the skilled person, and therefore not to repeat here.
The consumption of the present invention to described liquid steel dephosphorization agent is not particularly limited, and it usually should according to treating that dephosphorization molten steel is selected.Such as, described in per ton, treat dephosphorization molten steel, the consumption of described liquid steel dephosphorization agent can be 6-12kg, is preferably 7-10kg.
According to the method for liquid steel dephosphorization provided by the invention, as mentioned above, the Argon intensity in LF stove is at least 100Nm
3/ h ton molten steel, can ensure that phosphorus is fully removed with treating the phosphorus contained in dephosphorization molten steel fully to contact by described liquid steel dephosphorization agent like this, but consider from combined factors such as dephosphorization rate and Argon costs, preferably, the Argon intensity in LF stove is 120-160Nm
3/ h ton molten steel.
According to the method for liquid steel dephosphorization provided by the invention, the argon blowing time in LF stove should be as the criterion to be down within target level by the described phosphorus content treated in dephosphorization molten steel usually.As a rule, the argon blowing time in LF stove can be 4-6min.
In addition, in order to the phosphorus slag obtained after making dephosphorization is easily separated with molten steel, usually need to arrange electrically heated operation in LF stove.When described phosphorus slag viscosity not easily flows comparatively greatly, should open electrically heated operation to change slag, concrete operations are known to the skilled person.In addition, the actual conditions of described dephosphorization can be same as the prior art, and therefore not to repeat here.
In addition, after described molten steel completes dephosphorization in LF stove, usually also need to be introduced in RH stove to carry out refining, after composition, temperature are qualified, go up casting machine again cast, follow-up concrete operations all can be carried out according to existing method, and therefore not to repeat here.
Below will be described the present invention by embodiment.
In following examples and comparative example:
In molten steel, phosphorus content measures according to the method for regulation in GB/T223-82 " steel and alloy chemical analysis method ".
Containing the CaO of 98 % by weight in lime, all the other are CaCO
3; The grain graininess of described lime is all less than 30mm, and the grain graininess of 90 % by weight is 5-20mm.
Bauxitic clay contains the Al of 82 % by weight
2o
3, all the other are SiO
2.
Embodiment 1
This embodiment is for illustration of the method for liquid steel dephosphorization agent provided by the invention and liquid steel dephosphorization.
Certain factory 210t converter, tap 210t, in molten steel, oxygen activity actual measurement is 900ppm, and in molten steel, phosphorus content is 0.025 % by weight.In converter tapping process, add liquid steel dephosphorization agent 7kg/t steel with steel stream.Containing lime and bauxitic clay in liquid steel dephosphorization agent, and the content of lime is 92.5 % by weight, and the content of bauxitic clay is 7.5 % by weight.Moved in LF stove by molten steel after adding liquid steel dephosphorization agent and carry out dephosphorization, in LF operation, open electrically heated operation to be controlled by liquid steel temperature to change slag at 1580 DEG C, Argon intensity is 140Nm
3/ h ton molten steel, argon blowing time is 5min, then carries out taking off slag operation.After LF process terminates, in molten steel, phosphorus content is reduced to 0.0015 % by weight, and dephosphorization rate reaches 94%.Then the molten steel after LF stove refining treatment is carried out conventional RH stove refining, go up casting machine after composition, temperature are qualified again and cast.
Embodiment 2
This embodiment is for illustration of the method for liquid steel dephosphorization agent provided by the invention and liquid steel dephosphorization.
Certain factory 210t converter, tap 210t, in molten steel, oxygen activity actual measurement is 800ppm, and in molten steel, phosphorus content is 0.020 % by weight.In converter tapping process, add liquid steel dephosphorization agent 8kg/t steel with steel stream.Containing lime and bauxitic clay in liquid steel dephosphorization agent, and the content of lime is 95 % by weight, and the content of bauxitic clay is 5 % by weight.Moved in LF stove by molten steel after adding liquid steel dephosphorization agent and carry out dephosphorization, in LF operation, open electrically heated operation to be controlled by liquid steel temperature to change slag at 1590 DEG C, Argon intensity is 120Nm
3/ h ton molten steel, argon blowing time is 4min, then carries out taking off slag operation.After LF process terminates, in molten steel, phosphorus content is reduced to 0.0005 % by weight, and dephosphorization rate reaches 97.5%.Then the molten steel after LF stove refining treatment is carried out conventional RH stove refining, go up casting machine after composition, temperature are qualified again and cast.
Embodiment 3
This embodiment is for illustration of the method for liquid steel dephosphorization agent provided by the invention and liquid steel dephosphorization.
Certain factory 210t converter, tap 210t, in molten steel, oxygen activity actual measurement is 1000ppm, and in molten steel, phosphorus content is 0.022 % by weight.In converter tapping process, add liquid steel dephosphorization agent 6kg/t steel with steel stream.Containing lime and bauxitic clay in liquid steel dephosphorization agent, and the content of lime is 90 % by weight, and the content of bauxitic clay is 10 % by weight.Moved in LF stove by molten steel after adding liquid steel dephosphorization agent and carry out dephosphorization, in LF operation, open electrically heated operation to be controlled by liquid steel temperature to change slag at 1570 DEG C, Argon intensity is 160Nm
3/ h ton molten steel, argon blowing time is 6min, then carries out taking off slag operation.After LF process terminates, in molten steel, phosphorus content is reduced to 0.0015 % by weight, and dephosphorization rate reaches 93.2%.Then the molten steel after LF stove refining treatment is carried out conventional RH stove refining, go up casting machine after composition, temperature are qualified again and cast.
Embodiment 4
This embodiment is for illustration of the method for liquid steel dephosphorization agent provided by the invention and liquid steel dephosphorization.
Liquid steel dephosphorization is carried out according to the method for embodiment 1, unlike, in liquid steel dephosphorization agent used, the content of lime is 80 % by weight, and the content of bauxitic clay is 20 % by weight.After LF process terminates, in molten steel, phosphorus content is reduced to 0.002 % by weight, and dephosphorization rate reaches 92%.Then the molten steel after LF stove refining treatment is carried out conventional RH stove refining, go up casting machine after composition, temperature are qualified again and cast.
Embodiment 5
This embodiment is for illustration of the method for liquid steel dephosphorization agent provided by the invention and liquid steel dephosphorization.
Liquid steel dephosphorization is carried out according to the method for embodiment 1, unlike, in liquid steel dephosphorization agent used, the content of lime is 98 % by weight, and the content of bauxitic clay is 2 % by weight.After LF process terminates, in molten steel, phosphorus content is reduced to 0.003 % by weight, and dephosphorization rate reaches 88%.Then the molten steel after LF stove refining treatment is carried out conventional RH stove refining, go up casting machine after composition, temperature are qualified again and cast.
Comparative example 1
The liquid steel dephosphorization agent of this comparative example for illustration of reference and the method for liquid steel dephosphorization.
Liquid steel dephosphorization is carried out according to the method for embodiment 1, unlike, in liquid steel dephosphorization agent used, the content of lime is 50 % by weight, and the content of bauxitic clay is 50 % by weight.After LF process terminates, in molten steel, phosphorus content is reduced to 0.0055 % by weight, and dephosphorization rate reaches 78%.Then the molten steel after LF stove refining treatment is carried out conventional RH stove refining, go up casting machine after composition, temperature are qualified again and cast.
Comparative example 2
The liquid steel dephosphorization agent of this comparative example for illustration of reference and the method for liquid steel dephosphorization.
Liquid steel dephosphorization is carried out according to the method for embodiment 1, unlike, the Argon intensity in LF stove is 30Nm
3/ h ton molten steel.After LF process terminates, in molten steel, phosphorus content is reduced to 0.005 % by weight, and dephosphorization rate reaches 80%.Then the molten steel after LF stove refining treatment is carried out conventional RH stove refining, go up casting machine after composition, temperature are qualified again and cast.
Comparative example 3
This comparative example is for illustration of the method for the liquid steel dephosphorization of reference.
Certain factory 210t converter adopts converter " double slag process " disclosed in CN1995403A to smelt the steel grade of finished product carbon content≤0.005 % by weight.Although converter is at a large amount of auxiliary material of consumption and when deeply blowing serious, converter terminal molten steel phosphorus content is controlled 0.004 % by weight, but due to rephosphorization and alloy phosphorization, molten steel phosphorus content in steel is after rolling made to reach 0.0075 % by weight, follow-uply to operate without any dephosphorization, finally only change steel or melt down, losing larger.
As can be seen from the above results, liquid steel dephosphorization agent provided by the invention is adopted to carry out dephosphorization under specific Argon intensity, significantly can reduce the phosphorus content in molten steel, the dephosphorization rate of molten steel is improved, thus reduce converter smelting the burden in ultra-low phosphoretic steel water, have prospects for commercial application.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (7)
1. a liquid steel dephosphorization agent, is characterized in that, described liquid steel dephosphorization agent is made up of lime and bauxitic clay, and with the gross weight of described liquid steel dephosphorization agent for benchmark, the content of described lime is 90-95 % by weight, and the content of described bauxitic clay is 5-10 % by weight; With the gross weight of described lime for benchmark, containing the CaO of at least 95 % by weight in described lime, all the other are CaCO
3; With the gross weight of described bauxitic clay for benchmark, Al in described bauxitic clay
2o
3content be 80-85 % by weight, all the other are SiO
2.
2. liquid steel dephosphorization agent according to claim 1, wherein, the grain graininess of described lime is less than 30mm, and in described lime, the grain graininess of at least 80 % by weight is 5-20mm.
3. the method for a liquid steel dephosphorization, the method is included in converter tapping process, molten state treated that dephosphorization molten steel contacts with liquid steel dephosphorization agent, and product of contact is transferred in LF stove carries out dephosphorization, dephosphorization is skimmed after completing, it is characterized in that, described liquid steel dephosphorization agent is the liquid steel dephosphorization agent described in claim 1 or 2, and the Argon intensity in LF stove is at least 100Nm
3/ h ton molten steel.
4. method according to claim 3, wherein, described in treat the oxygen activity >=500ppm of dephosphorization molten steel; Describedly treat that the phosphorus content of dephosphorization molten steel is 0.01-0.03 % by weight.
5. method according to claim 4, wherein, treats dephosphorization molten steel described in per ton, and the consumption of described liquid steel dephosphorization agent is 6-12kg.
6. method according to claim 3, wherein, the Argon intensity in LF stove is 120-160Nm
3/ h ton molten steel.
7. the argon blowing time according to the method in claim 3-6 described in any one, wherein, in LF stove is 4-6min.
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| CN104195290A (en) * | 2014-09-15 | 2014-12-10 | 攀钢集团西昌钢钒有限公司 | Molten steel dephosphorization agent and molten steel dephosphorization refining method |
| CN104561434A (en) * | 2014-12-31 | 2015-04-29 | 南阳汉冶特钢有限公司 | Low-phosphorus steel smelting process |
| CN107746907B (en) * | 2017-10-31 | 2019-11-08 | 攀钢集团攀枝花钢铁研究院有限公司 | The production method of clean steel |
| CN107557534A (en) * | 2017-10-31 | 2018-01-09 | 攀钢集团攀枝花钢铁研究院有限公司 | The production method of extremely low phosphoretic steel |
| CN107723415B (en) * | 2017-10-31 | 2019-05-10 | 攀钢集团攀枝花钢铁研究院有限公司 | The production method of the ultralow phosphorus ultra-low-carbon steel of super-low sulfur |
| CN109207672B (en) | 2018-12-03 | 2020-02-04 | 南阳汉冶特钢有限公司 | Slag discharging method in production process of ultra-low phosphorus steel and production method of ultra-low phosphorus steel |
| CN110468255A (en) * | 2019-09-06 | 2019-11-19 | 鞍钢股份有限公司 | A kind of free-floride KR desulfurizing agent and its preparation, application method |
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| JP3297997B2 (en) * | 1998-02-26 | 2002-07-02 | 住友金属工業株式会社 | Hot metal removal method |
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| CN1618992A (en) * | 1999-12-29 | 2005-05-25 | 张梦显 | Outside of furnace refining agent and its manufacturing method |
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